KR101785241B1 - Prepreg made from monomer of polyethersulfone polymer and method for manufacturing same - Google Patents

Abstract

The present invention relates to a prepreg made from a monomer of a polyethersulfone polymer and a method of preparing the same, and more particularly, to a prepreg prepared from a monomer of a polyether sulfone polymer, An epoxy resin mixture comprising an alkyne monomer and an azide monomer containing an azide group (-N ₃ ), a curing agent and an epoxy resin is coated or impregnated on the reinforcing fiber, There is provided a prepreg which provides excellent interlayer fracture toughness in the production of a prepreg composite due to an epoxy resin mixture in which a polyethersulfone based polymer is uniformly dispersed as a toughening agent obtained by polymerizing the above two types of monomers .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg made from a monomer of a polyethersulfone type polymer and a method for producing the prepreg,

The present invention relates to a prepreg prepared by using an epoxy resin mixture containing an azide monomer and an alkyne monomer, which are two kinds of monomers capable of forming a polyether sulfone polymer.

Prepreg is an abbreviation for Pre-impregnated Composite Fibers. It is a sheet type product in which a certain amount of matrix resin such as polymer resin is impregnated in reinforced fiber. This prepreg is used as an intermediate material of a composite material. Prepreg is a semi-hardened product impregnated with resin, which is formed by laminating several prepregs according to the purpose of use and applying a constant temperature and pressure to completely harden the resin.

Carbon fibers, glass fibers, fibers and the like having high strength and elasticity are used as ordinary reinforcing fibers, and various kinds of thermoplastic resins and thermosetting resins are used as binders.

Composite materials prepared using such prepregs are superior to other materials in terms of strength, stiffness, corrosion resistance, fatigue, wear resistance, impact resistance, Weight reduction, and the like, and recently it has been widely used in the production of aerospace industry, general industry, sports leisure goods, and the like.

Epoxy resin, which is one of the most widely used resins in prepreg manufacturing, is a thermosetting resin and can change various physical properties and can stand at an extreme temperature. In addition, it has advantages such as durability against excellent fatigue load, moisture absorption property, volume shrinkage, moisture resistance, chemical resistance and the like, which are obtained from reduction of weight of a structure. However, epoxy resin, which is a thermosetting polymer, tends to be limited in the use of a structural material used for receiving a load because of its low fracture toughness because it is brittle. Fracture toughness is a measure of how much the material can resist during or after cracking.

As the epoxy resin is modified by adding a toughening agent or the like, fracture toughness can be improved, and thus a thermoplastic polymeric toughening agent is widely used in the epoxy resin. In particular, US Patent No. 4,656,207 discloses a polyether sulfone polymer toughening agent as an effective toughening agent capable of improving the fracture toughness of an epoxy resin.

In general, in order to use a polyether sulfone polymer as a toughening agent, it is necessary to uniformly disperse a polyether sulfone polymer in an epoxy resin. In this process, it is necessary to add heat for a certain period of time, . When the polyether sulfone polymer is added to the epoxy resin, there is a problem that the viscosity of the mixture is greatly improved. When the viscosity is increased, a problem in forming the prepreg may arise and molding of the prepreg may be difficult. Particularly, in a continuous prepreg system that mass-produces an epoxy resin mixture, it is difficult to apply a process to a prepreg system because of such problems.

The present invention relates to a polysulfone-based polymer toughened epoxy resin composition containing a polysulfone-based polymeric toughening agent, which is a prior-filed invention of the present inventor and Korean Patent Application No. 10-2015-0155218, It is the filing invention.

U.S. Patent No. 4,656,207

An azide-based monomer to the present invention comprises a polyether sulfone-alkyne-based monomers including a monomer of an ether group and sulfone group of two that can form a polymer (alkyne monomer) with an azide group (-N ₃₎ ( azide monomer) and a curing agent in an epoxy resin to prepare an epoxy resin mixture, and to provide a prepreg using the epoxy resin mixture and a method for producing the prepreg.

The prepreg of the present invention for solving the above object is a monomer of a polyether sulfone type polymer and is an alkene type monomer containing ether group and sulfonic group in one molecule which are two kinds of monomers capable of forming polyether sulfone type polymer An epoxy resin mixture comprising an alkyd monomer, an azide monomer containing an alkyne monomer and an azide group (-N ₃ ), a curing agent and an epoxy resin is coated or impregnated on the reinforcing fiber .

The content of the alkyne-based monomer and the azide-based monomer in the epoxy resin mixture is preferably 40 wt% or less based on the total weight of the epoxy resin when the polyether sulfone-based polymer is formed. The content of the curing agent is 1 equivalent of the epoxy resin Based on the total amount of the curing agent. Here, the content of the curing agent can be appropriately adjusted according to the content of the epoxy resin, and is not particularly limited to the above-mentioned range.

The alkyne monomer, which is one of the two monomers capable of forming the polyether sulfone polymer, is preferably sulfonylbis (propynyloxy) benzene (hereinafter also referred to as "SPB"), 4-sulfonylbis ((prop-2-yn-1-yloxy) benzene).

[Chemical Formula 1]

The 4,4'-sulfonylbis ((prop-2-yn-1-yloxy) benzene) is etherified with 4,4'-sulfonyldiphenol and propargyl bromide, And then synthesized and reacted. In the synthesis, tetrahydrofuran (THF) may be prepared by reacting calcium carbonate (K ₂ CO ₃ ) together with a solvent.

[Reaction Scheme 1]

The azide monomer, which is another one of the two monomers capable of forming the polyether sulfone polymer, may be an alkyl azide monomer, an alkene azide monomer, an alkyne azide monomer, or the like, Azide-based benzene, azide-based benzene derivatives, and the like.

Specific examples of the azide-based benzene monomer include 1,4-bis (azidomethyl) benzene (p-BAB) represented by the following formula 2, 1,3-bis (azidomethyl) benzene (m- , 1,3,5-tris (azidomethyl) benzene (TAB) represented by the following formula (4) can be used.

At this time, each azide-based monomer may be used singly or in combination of two or more as necessary.

(2)

(3)

[Chemical Formula 4]

The azide type compounds such as 1,4-bis (azidomethyl) benzene (p-BAB), 1,3-bis (azidomethyl) benzene (m- The azide monomer forms a polyether sulfone polymer by polymerization with an alkyne monomer, 4,4'-sulfonylbis (prop-2-yn-1-yloxy) benzene, Poly (p-BAB / SPB), poly (m-BAB / SPB) and poly (TAB / SPB), respectively.

For example, a 4,4'-sulfonylbis ((prop-2-yn-2-yn-2-yn- 1-yloxy) benzene is polymerized to form poly (p-BAB / SPB) represented by the following formula 5, and 1,3-bis (azidomethyl) benzene (m- (prop-2-yn-1-yloxy) benzene) to form poly (m-BAB / SPB) represented by the following formula 6: 1,3,5-tris (azidomethyl) benzene ) And 4,4'-sulfonylbis ((prop-2-yn-1-yloxy) benzene) may be polymerized to form poly (TAB / SPB)

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the general formulas (5) to (7), n is an integer of 1 to 100. N is a structural repeating unit of the formula and may vary depending on the reaction conditions. For example, 1,4-bis (azidomethyl) benzene (p-BAB) and 4,4'-sulfonylbis (P-BAB / SPB) polymerized at 90 ° C at a temperature of 90 ° C can have an average n of 3 to 7 and can be synthesized at 180 ° C under another polymerization reaction temperature condition, The average n of the polyether sulfone-based polymer poly (p-BAB / SPB) may be between 5 and 10.

In the present invention, the epoxy resin is not particularly limited as long as it is a bifunctional or more functional epoxy resin having two or more epoxy groups.

Specific examples of the epoxy resin include diglycidyl ether of bisphenol-F (DGEBF) and bisphenol-A diglycidyl ether of bisphenol A as a bifunctional epoxy resin, DGEBA), triglycidyl p-aminophenol (TGAP) and triglycidyl m-aminophenol (TGAP) can be used as the trifunctional epoxy resin, and tetrafunctional N, N, N ', N'-tetramlycidyl-4,4'-diaminodiphenylmethane (TGDDM) as an epoxy resin, May be used alone or in combination of two or more kinds of these epoxy resins.

As the curing agent of the epoxy resin mixture of the present invention, an aromatic amine curing agent can be used. As the curing agent, diaminodiphenylsulfone (DDS), metaphenyldiamine (MDP), diaminadiphenylmethane , And DDM). Among them, diaminodiphenylsulfone (DDS) is more preferably used.

Wherein the reinforcing fiber is selected from the group consisting of carbon fiber, glass fiber, aramid fiber, basalt fiber, boron fiber and polyester fiber. One or more of them can be used, and carbon fibers can be preferably used. Any reinforcing fiber that can be used by those skilled in the art can be used without limitation.

There are no particular restrictions or limitations on the form of such reinforcing fibers, and various types of fibers can be used, including, for example, unidirectionally arranged long fibers, braids, short fibers, nonwoven fabrics and cut fibers.

In addition, the epoxy resin mixture may further include a thermoplastic reinforcing agent, wherein the thermoplastic reinforcing agent is capable of synergy with the polyether sulfone, that is, when the composite material is finally molded with the prepreg, It is preferable to select a polymer series capable of reacting with the epoxy resin as a polymer series capable of improving the physical properties of the toughness of the composite material.

The thermoplastic toughening agent specifically includes, for example, polyamide, copolyamide, polyketone, polyetheretherketone (PEEK), polyester, polyurethane polyurethane and polytetrafluofethylene (PTFE), derivatives thereof, or a combination thereof may be used. As the thermoplastic toughening agent of the present invention, polyamide may be preferably used.

In order to accomplish the above object, the prepreg of the present invention includes two types of monomers capable of forming a polyether sulfone polymer, which include ether groups and sulfone groups in one molecule (Azide monomer) containing an alkyne monomer and an azide group (-N ₃ ) is dispersed in an epoxy resin and dispersed evenly, and at the same time, the mixture is mixed at a predetermined temperature so that the polymerization reaction proceeds to form a first epoxy (S120) of preparing a second epoxy resin mixture by adding a curing agent to the prepared first epoxy resin mixture and mixing the prepared second epoxy resin mixture to form a second epoxy resin mixture, And impregnating the impregnated prepreg to prepare a prepreg (S130).

The step (S110) of preparing the first epoxy resin mixture may be carried out at a temperature of 5 ° C to 200 ° C using an azide monomer (azide monomer) containing an epoxy resin, an alkyne monomer and an azide group (-N ₃ ) monomer may be uniformly mixed to form a first epoxy resin mixture. The alkyne monomer and the azide monomer are preferably reacted at a temperature of 90 ° C to 200 ° C at which polymerization reaction of the alkyne monomer and the azide monomer occurs to form a polyether sulfone polymer. At this time, the polymerization reaction between the alkyne-based monomer and the azide-based monomer becomes shorter as the reaction temperature increases. For example, when the polymerization is carried out in the epoxy resin at 90 ° C, the polymerization reaction time And a polymerization reaction time of about 3 hours in the epoxy resin is required at the reaction at 180 ° C.

Therefore, when the polymerization temperature is lower than 90 ° C, the process time becomes longer and the polymerization reaction does not occur properly. On the contrary, if the temperature is higher than 200 ° C, the first epoxy resin mixture is cooled before the second epoxy resin mixture preparation step The process efficiency is not good because a relatively high cooling temperature is required.

The polymerization of the alkyne-based monomer and the azide-based monomer, which are monomers of the polyether sulfone-based polymer, is not limitedly completed only in the step of producing the first epoxy resin mixture (S110), but the second epoxy The polymerization reaction can also proceed in the step of preparing the resin mixture (S120) and the step of preparing the prepreg (S130).

In addition, the polyether sulfone-based polymer can be polymerized even when a plurality of prepregs are laminated using the prepreg produced in the present invention to form a prepreg composite.

In the step (S110) of preparing the first epoxy resin mixture, a monomer of the polyether sulfone polymer may be inserted, and then a thermoplastic strengthening agent may be separately added.

In the step S120 of manufacturing the second epoxy resin mixture, the first epoxy resin mixture prepared through the step S110 of manufacturing the first epoxy resin mixture is cooled to a temperature lower than the curing start temperature of the second epoxy resin mixture And the like. That is, when the curing agent is added, it is preferable to lower the temperature of the epoxy resin mixture to a temperature lower than the curing start temperature in consideration of the curing reaction initiation temperature, and then to inject the curing agent so that the curing reaction does not progress rapidly.

Here, the curing reaction temperature at which the curing is actively performed is 150 ° C or higher, and the curing reaction of the epoxy resin and the curing agent of the epoxy resin mixture may actively take place in the temperature range of 150 ° C to 230 ° C. Therefore, after the temperature of the first epoxy resin mixture is lowered to less than 150 캜, a curing agent is added to prepare a second epoxy resin mixture. The preferred temperature for warming the first epoxy resin mixture is preferably less than 80 캜, which is considered to be almost no activity of the curing agent.

The epoxy resin mixture thus prepared can proceed simultaneously with the polymerization reaction of the monomer of the polyether sulfone type polymer and the curing reaction of the epoxy resin mixture without affecting the reaction of each other. The curing reaction of the epoxy mixture may proceed in part during the preparation of the prepreg (S130), or may be completely terminated during molding of the composite using the completed prepreg.

The method for preparing the prepreg by coating or impregnating the reinforcing fiber with the second epoxy resin mixture prepared as described above in the step of preparing the prepreg (S130) is not particularly limited, Can be prepared according to the method. Specifically, for example, the prepreg of the present invention can be produced by a solvent method or a hot-melt method.

Generally, the solvent method is a method of preparing a prepreg by dissolving a resin in a solvent and impregnating the resin into a reinforcing fiber to enhance the impregnation property of the resin composition with respect to the reinforcing fiber. In another method, the hot- Is directly impregnated into the reinforcing fiber to prepare a prepreg.

On the other hand, description of constituent components such as an alkyne monomer, an azide monomer, a curing agent, an epoxy resin, a reinforcing fiber and a thermoplastic toughening agent used in the prepreg manufacturing method of the present invention, Are the same as those in the prepreg according to the present invention, and a duplicate description will be omitted.

The prepreg prepared in the present invention can be completely cured at 180 ° C for 2 hours to 5 hours, and is preferably cured at 150 ° C or higher and 250 ° C or lower. If the temperature is less than 150 ° C, epoxy hardening may not occur completely, and the properties such as tensile strength of the prepreg composite may be deteriorated. When the epoxy resin is cured at a temperature exceeding 250 ° C, decomposition of the epoxy may occur.

In the present invention, a polyether sulfone polymer is dispersed in an epoxy resin by using a monomer of a polyether sulfone polymer which is easier to disperse than a general polyether sulfone polymer used as a toughening agent, The legs can be easily manufactured.

In addition, when the prepreg of the present invention is used in the preparation of prepreg-based composites, it can provide excellent interlaminar fracture toughness. Further, there is an effect that the heat resistance can be maintained without any problem such as lowering of the glass transition temperature (Tg) which can be exhibited when the conventional toughening agent is applied.

1 is a flow chart of a prepreg manufacturing method of the present invention.
2 is a photograph of a cured specimen of an epoxy resin mixture according to Example 1 of the present invention, observed through a scanning electron microscope (SEM).

Technical terms used herein should be interpreted in a sense that is generally understood by a person skilled in the art to which the present invention belongs, unless otherwise defined with special meaning in the present invention, And shall not be construed as an oversimplified meaning. In addition, the general terms used in the present invention should be construed in accordance with the predefined or prior context.

Also, the singular forms "as used herein include plural referents unless the context clearly dictates otherwise. That is, the terms 'comprising,' 'comprising,' or 'including,' as used herein, should not be construed as necessarily including the various components or steps described in the specification, It is to be understood that the components or some steps may not be included, or may include additional components or steps.

The term " first epoxy resin mixture " and " second epoxy resin mixture " are terms used for the purpose of distinguishing an epoxy resin mixture formed in each step. Refers to a mixture obtained by mixing a monomer of an epoxy resin and a polyether sulfone polymer, and "a second epoxy resin mixture" means a mixture obtained by mixing a curing agent into the first epoxy resin mixture.

Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples. It is to be understood that these examples and comparative examples are illustrative examples of the present invention, Therefore, the present invention is not limited to the examples and comparative examples described herein.

Examples 1 and 2 and Comparative Examples 1 and 2 to be described below are a step (S110) of preparing a first epoxy resin mixture in the method for producing a prepreg of the present invention for evaluating physical properties of an epoxy resin mixture, (S120) to prepare a second epoxy resin mixture.

≪ Example 1 >

Example 1 was repeated except that 100 g of triglycidyl p-aminophenol (TGAP), which is a trifunctional epoxy resin, was used as an epoxy resin, and 5 g of 5 wt% (5 g) of poly 1-y-1-yloxy) benzene, which can form 1,3-bis (m-BAB / SPB), with 4,4'-sulfonylbis (prop- Into a epoxy resin and mixed at 90 DEG C for about 1 hour until uniformly dispersed to form a first epoxy resin mixture. The first epoxy resin mixture thus formed was heated to 70 ° C, and then a diaminodiphenylsulfone (DDS) as a curing agent was added thereto and mixed to prepare a second epoxy resin mixture.

≪ Example 2 >

100 g of triglycidyl p-aminophenol (TGAP), which is a trifunctional epoxy resin, is used as the epoxy resin. The monomer of the polyether sulfone type polymer is 1,4-bis (azidomethyl) benzene (p-BAB), 1,3,5-tris (azidomethyl) benzene (TAB) and 4,4'- poly (p-BAB / SPB) and poly (TAB / SPB) formed by polymerization at a molar ratio of 9: 1: 10.5 based on the total weight of the epoxy resin (5 g) is formed, and the mixture is added to 100 g of epoxy resin and mixed at 90 DEG C for about 1 hour to form a first epoxy resin mixture. The first epoxy resin mixture thus formed was heated to 70 ° C, and then a diaminodiphenylsulfone (DDS) as a curing agent was added thereto to prepare a second epoxy resin mixture.

≪ Comparative Example 1 &

In Comparative Example 1, 5 wt% polyethersulfone (PES) (solvay, Mw = 15,000 g / mol, based on the total weight of the epoxy resin, triglycidyl p-aminophenol ) Was mixed at 130 ° C. for about 1 hour, and the mixture was warmed to 70 ° C., and diaminodiphenylsulfone (DDS) as an amine curing agent was added thereto and mixed at 130 ° C. for about 1 hour to prepare an epoxy resin mixture.

≪ Comparative Example 2 &

In Comparative Example 2, diaminodiphenylsulfone (DDS), which is an amine curing agent, is added to triglycidyl p-aminophenol (TGAP) with an epoxy resin at 70 ° C to prepare an epoxy resin mixture.

The epoxy resin mixture prepared for the evaluation of physical properties of the epoxy resin mixture prepared in Examples 1 to 2 and Comparative Examples 1 and 2 was cured in an oven at 180 ° C for 3 hours to prepare an epoxy specimen, And the results are shown in Table 1 below.

The glass transition temperature (Tg) was measured by differential scanning calorimetry (DSC) to determine the thermal and mechanical properties of the prepared epoxy specimens.

In addition, the fracture toughness (K _IC ) value of the epoxy specimen was measured according to ASTM D5045 by resistance to crack propagation as a parameter indicating the sensitivity of the material strength.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 K _IC (MN · m ^3/2 ) 1.86 1.58 1.05 0.9 T _g (° C) 200.21 244.78 232.24 233

As shown in Table 1, the fracture toughness values of Examples 1 and 2 were 1.5 MN · m ^3/2 or more, which was greatly increased compared to the fracture toughness values (K _IC ) of Comparative Examples 1 and 2 And the glass transition temperature (Tg) of the examples were similar to those of the comparative example. This indicates that the heat resistance is maintained without the problem of decreasing the glass transition temperature (Tg) of the conventional toughening agent .

FIG. 2 is a photograph of a cross section of the epoxy specimen prepared in Example 1 by a scanning electron microscope (SEM). As shown in FIG. 2, a polyether sulfone-based polymer (poly -BAB / SPB) was uniformly dispersed.

Example 3 and Comparative Example 3 described below are for evaluating the physical properties of a prepreg applying an epoxy resin mixture, and a step (S110) of preparing a first epoxy resin mixture of the present invention and a step (S110) of preparing a second epoxy resin mixture And a step (S 130) of preparing a prepreg by coating or impregnating the reinforcing fiber with the second epoxy resin mixture prepared through the manufacturing step (S120).

≪ Example 3 >

In Example 3, 60 g of diglycidyl ether of bisphenol-A (DGEBA) and 40 g of triglycidyl p-aminophenol (TGAP) were prepared by the prepreg method of the present invention, Bis (azidomethyl) benzene (p-BAB / SPB) capable of forming 5 wt% (5 g) of poly (p-BAB / SPB) based on the total amount of epoxy resin, BAB) and 4,4'-sulfonylbis (prop-2-yn-1-yloxy) benzene were mixed with the epoxy resin at a molar ratio of 1: 1 at 130 ° C for about 1 hour, and then thermoplastic strengthening agent Polyamide (Nylon 66 ) Are added and mixed until evenly dispersed to form a first epoxy resin mixture. After the first epoxy resin mixture thus formed is heated to 70 캜, a diaminodiphenylsulfone (DDS) as a curing agent is finally added to form a second epoxy resin mixture.

The resulting epoxy resin mixture is then rolled up on a release paper to produce a prepreg, wherein the amount of epoxy resin per unit area is 53 ± 2 g / m ² . Then, two resin papers thus prepared were placed on top of unidirectional carbon fibers in a sheet form and laminated. Then, the resin paper was heated and pressed at a temperature higher than the melting point of the resin paper to about 120 ° C, impregnated with resin, do. At this time, the prepreg has an amount of carbon fiber per unit area of 165 ± 2 g / m ² .

≪ Comparative Example 3 &

In Comparative Example 3, 60 g of diglycidyl ether of bisphenol-A (DGEBA) and 40 g of triglycidyl p-aminophenol (TGAP) were used to make 100 g of total epoxy resin And 5 wt% (5 g) of polyethersulfone (PES) (solvay, Mw = 15,000 g / mol) was added to the mixture at 130 ° C for about 1 hour based on the total amount of the epoxy resin, (Nylon 66), and the mixture was stirred for about 1 hour until uniformly dispersed. After the temperature of the resin mixture was reduced to 70 ° C, diaminodiphenylsulfone (DDS) as a curing agent was finally added thereto to prepare an epoxy resin mixture .

The resulting epoxy resin mixture is then rolled up on a release paper to produce a prepreg, wherein the amount of epoxy resin per unit area is 53 ± 2 g / m ² . Then, two resin papers thus prepared were placed on top of unidirectional carbon fibers in a sheet form and laminated. Then, the resin paper was heated and pressed at a temperature higher than the melting point of the resin paper to about 120 ° C, impregnated with resin, do. At this time, the prepreg has an amount of carbon fiber per unit area of 165 ± 2 g / m ² .

Prepregs prepared in Example 3 and Comparative Example 3 were autoclaved at 180 ° C for 2 hours to prepare prepreg composites. The resultant prepreg composite was subjected to an interlaminar fracture toughness test (G _IIC test) according to ASTM D7905. The results are shown in Table 2 below, and the _GIC values shown in Table 2 are for the resistive energy against the propagation of interlaminar cracks.

division Example 3 Comparative Example 3 G _IIC (in-lbf / in ² ) 7.85 5.60

As shown in Table 2, the interlaminar fracture toughness value of Example 3 was 7.85 in-lbf / in ² , which was significantly increased compared to the interlayer fracture toughness value of 5.60 in-lbf / in ² of Comparative Example 3.

Therefore, as described above, the prepreg with the epoxy resin mixture according to the present embodiment is effective for improving the interlaminar fracture toughness in the formation of the composite material, which is the same as the fracture toughness K of Examples 1 to 3 shown in Tables 1 and 2 _IC and interlaminar fracture toughness G _IIC .

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory only and are not to be construed as limiting the scope of the invention as disclosed in the accompanying claims. Therefore, the scope of the present invention is not limited thereto. It will be apparent to those skilled in the art that various changes, substitutions, and alterations can be made hereto without departing from the spirit of the present invention, and it is obvious that those parts easily changeable by those skilled in the art are included in the scope of the present invention.

Claims (7)

Sulfonylbis ((propynyloxy) benzene), which is an alkyne monomer containing an ether group and a sulfonic group in one molecule, and an azide group (-N ₃ (P-BAB), 1,3-bis (azidomethyl) benzene (m-BAB) and 1,3,5-tris (azidomethyl) benzene At least one azide monomer;
Curing agent; And
Wherein the reinforcing fiber is coated or impregnated with an epoxy resin mixture comprising an epoxy resin. The method according to claim 1,
The alkyne monomer, sulfonylbis (propynyloxy) benzene, is synthesized by etherification reaction of 4,4'-sulfonyldiphenol with propargyl bromide. . The method according to claim 1,
Wherein the polyether sulfone-based polymer comprises at least one or more repeating units represented by the following general formulas (5) to (7).
[Chemical Formula 5]

[Chemical Formula 6]

(7)

(In the above Chemical Formulas 5 to 7, n is an integer of 1 to 100) Polyether sulfone and Ain sulfonylbis ((propynyloxy) benzene) alkynyl monomer (alkyne monomer) containing an ether group and sulfone group in one molecule as the second monomer capable of forming a polymeric azide group (-N ₃₎ (P-BAB), 1,3-bis (azidomethyl) benzene (m-BAB) and 1,3,5-tris (azidomethyl) benzene Preparing a first epoxy resin mixture by mixing at least one azide monomer into an epoxy resin;
Preparing a second epoxy resin mixture by adding a curing agent to the prepared first epoxy resin mixture and mixing them; And
And preparing a prepreg by coating or impregnating the prepared second epoxy resin mixture on the reinforcing fiber. 5. The method of claim 4,
And cooling the prepared first epoxy resin mixture to a temperature lower than the curing start temperature of the second epoxy resin mixture before the step of preparing the second epoxy resin mixture. 5. The method of claim 4,
The alkyne monomer, sulfonylbis (propynyloxy) benzene, is synthesized by etherification reaction of 4,4'-sulfonyldiphenol with propargyl bromide. ≪ / RTI > 5. The method of claim 4,
Wherein the polyether sulfone-based polymer comprises at least one of repeating units represented by the following Chemical Formulas (5) to (7).
[Chemical Formula 5]

[Chemical Formula 6]

(7)

(In the above Chemical Formulas 5 to 7, n is an integer of 1 to 100)

Images